Vinyl chloride resins plasticized with diester-amides



June 14, 1949. F. JOHNSTON ETAL 2,472,900

VINYL CHLORIDE'RESINS PLASTICIZED WITH DIESTER-AMIDES Original Filed May 1, 1946 PROPERTIES OF'VINYL CHLORIDE-VINYL ACETATE COPOLYMERS PLASTICIZED WITH COMPOUNDS K C H OOCR RC0 N CZH4OOCR FLEX TEMPERATURE T '0 I l PART/AL V INCOMPA TIBLE [0 DAY EXTRACTION FROM 0.004 IN. FILM AT 2507.

3'4 5 6'7 8 9 lo l2 l3 NO. OF CARBON ATOMS IN RCO- INVENTORS FRANKLIN JOHNSTON WILL/4M H. HENSLEV Patented June 14, 1949 I UNITED STATES; PATENT. omcs VINYL CHLORIDE aasms m wrrn DIESTER-AMIDE STICIZED Franklin Johnston and William H. Hensley, St.

Albans, W. Va., alsignors to Carbide and Carbon Chemicals Corporation, a corporation of New York Original application May 1, 1946, Serial No.

Divided and this application August 27, 1947, Serial No. 110,884 Claims. (01. zoo-41.2)

I The expanding use of vinyl chloride resins has created a need for better plasticizers to be incorporated with such materials. Plasticizers are required, forlnstance, to reduce the molding temperature of vinyl chloride resins, and to increase the flexibility of films, which may be calendered, cast, or deposited from lacquers. Also, plastiagents which have been prepared fromalkylolamines and higher fatty acids, such as lauric and cizers are incorporated in rather large amount with certain vinyl chloride resins to form resilient elastomeric compositions which have a host of applications. There are many properties which are desired in plasticizers; they should have extensive compatibility or soivating power for a wide range of synthetic resins, they should resist extraction by oils or water, and they should not exude or "sweat-out from plastic compositions nor should they gradually volatilize or migrate to other objects in contact with the plastic compo sitions. It is also important that plasticizers be stable at elevated temperature so that they do not release noxious fumes during compounding on the mill. In addition plasticizers should be non-toxic, non-corrosive, and free from objectionable odor. Furthermore, plasticizers should retain their eflectiveness as low temperatures so that plasticized compositions do not become brittle in frigid weather.

To date, to our knowledge, no organic chemist has succeeded in making an "ideal" plasticizer for vinyl chloride resins, which is perfect in all respects, nor do we claim to have done this, but

we have succeeded in developing a class of compounds which have outstanding utility as plasticizers for vinyl chloride resins, and which are superior in many respects to presently used materials. Our compounds are diester amides represented by the formula CrHgRxOOOR RCO-N cimaioocn where R is an alkyl radical containing from 2 to 8 carbon atoms inclusive and R1 is hydrogen or methyl. These compounds maybe prepared by heating one mol of diethanplamine, diisopropanolamine, or N-hydroxyethyl, N-hydroxyisopropyl amine with at least three moles of a fatty acid containing from 3 to 9 carbon atoms; ,The resulting diester-amides are stable high-boiling liquids which are non-basic and which do not form salts. Likewise they are water-insoluble and contain no hydrophylic groups, so that they are not dispersing agents; Thus,-they-are to be distinguished from the many types of dispersing stearic acids.

One of the outstanding properties of the new compounds is their eflectiveness as plasticizers for copolymers of vinyl chloride and vinyl acetate.

In this respect, it has been found that the number of carbon atoms in the radical RC0- is of vital,signiflcance as shown in the drawing. This drawing shows how the properties of vinyl chloride-vinyl acetate copolymers plasticized with diester-amides of diethanolamine vary with the number of carbon atoms in the acyl radical RCO. The percentage of plasticizer is'cho'sen so that the elongation of a test piece under a load of 1,000 lbs. per sq. in. at C. (applied at a constant rate in 74 seconds) is 100%. When the acyl radical is acetyl, the compound is only partially compatible with vinyl chlorideevinyl acetate copolymers. By "partial compatibility is meant that the compound can be mixed with Y the resin on aheated rubber mill to yield a flexflexibility of the plasticized compositions increases ,as the number of carbon atoms in the acyl radical increases, as shown in the drawing of Flex Temperature vs. No. of Carbon Atoms in RCO. The flex temperature is a measure of pliability and is defined as the temperature which yields an apparent modulus of elasticity of 135,000 lbs. per

sq. in. according to the work of Clash and Berg. Ind. Eng. Chem. 34, 1218 (1942). The extracftion of plasticizer by water decreases markedly as the number of carbon atoms-in the acyl radical increases, while the extraction by mineral oil increases somewhat. The extraction of plasticizer by oils is also dependent on the molecular configuration of the alkyl radical in RCO--. For the same number of carbon atoms in the allwl radical, the percentage extraction by oil is less when R is a branched-chain alkyl radical than when R. is normal alkyl.

Our preferred. plasticizer is the diester-amide prepared from diethanolamine and 2-ethylhex- 3 anoic acid. having the chemical name, 2,2'(2- ethylhexanamidoldiethyl dii2-ethylhexanoate) hereafter referred to, for convenience, as the 2- ethylhexyl diester-amide. This compound has a high degree 01' compatibility with copolymers of vinyl chloride and vinyl acetate and may serve as a coupling agent so that less compatible modiiying materials may be included-in compositions containing these copolymers. The 2-ethylhexyl diester-amide may-be mixed more rapidly with copolymers oi vinyl chloride and vinyl acetate on a heated rubber mill at'temperatures of 140 to 160 C. than is the case with other materials, so that production costs are decreased and the heat ing that the 2-ethylhexyl diester-amide is superior in most respects to two standard compounds, tricresyl phosphate and di(2-ethylhexyl) phthalate as a plasticizer for vinyl chloride resins. The tests were performed using a commercial grade of a copolymer of vinyl chloride and vinyl acetate containing about 96% vinyl chloride, and having an average molecular weight 01 about 23,000 to 24,000, according to the method reported by Douglas and Stoops, Ind. 81 Eng. Chem. 28 1152 (1936), commercial grades of the two reference plasticizers, and a highly refined sample oi the fl-ethylhexyl diester-amide. The results of the tests were as follows:

Elongation per cent a g g a g 2 fllm in- F1 Per Cent Plasticirer 1 Tom By Wt. All Water 011 C. 25 0. 40 C. at at at i 60 0. 26 C. 25 C.

Tricrssyl phosphate 35.3 100 218 0. ii 1. 0 l. 5 +4. 2 Di (2-ethylhexy1) phthalata. 33.5 47 100 187 0. 7 0.3 8. 2 -16.0 2-Ethylhexyl diester-amidee. 35. 0 56 100 165 0. 3 0. 1 l0. 3 m. 0

l The percentage oi plasticizer is chosen so that the elongation of a test piece under a load of 1,000 lbs. per sq. in. at 0. (applied at a constant rate in 74 seconds) is 100 per cent.

sensitive copolymersv are subjected to elevated temperatures for shorter periods. The proportion of plasticizers which may thus be incor- 3o porated may vary from about 10% toabout 50% oi. the composition, (resin plus plasticizer), and the resulting products vary from flexible films to resilient elastomeric sheet material, depending on proportion of plasticizer.

merized vinyl chloride resins. These dispersions o crease in extensibility on hot days.

or pastes are prepared by grinding the emulsion polymerized resins with the plasticizer, with or without the addition of mixtures of hydrocarhon diluents and ketone solvents having controlled swelling action in the resin, in a ball-mill or like apparatus. If the plasticizer alone is employed as the dispersing medium, about 40 to 60% of the plasticizer by weight of the composition is required, whereas if the said mixtures are included, the proportions of plasticizer may be adjusted to that required for the desired flexibility of the final product. These dispersions or pastes may be subjected, while fluid, to a iorming process, as by casting or molding, and then set in the desired form by the application oi heat and cooling. During heating, the volatile mixtures of hydrocarbons and solvents, if used, are driven off; but the plasticizer is retained and unintentional losses thereof are to be avoided. The 2-ethylhexyl dlester-amide has a low vapor pressure and is not driven ofi durin: such fusing operations. For instance, the

. vapor pressure of the 2-ethylhexyl diesteramide at 200 C. is 0.6 mm. Hg, whereas the vapor pressure of di(2-ethylhexyl) phthalate. a plasticizer which is currently used in such dispersions, is 1.35 mm. Hg at 200 .C. In additionto its low volatility, the 2-ethylhexyl diester-amide persions or pastes.

Comparative tests have been carried out show- Itwill be observed that the compositions containing the 2-ethylhexyl diester-amide show less change in elongation with temperature than do the other compositions. Thus, the slope of the elongation-temperature curves (taken as the ratio of elongation at 40 C. to that at 10 C.) is 3 for compositions containing the 2-ethylhexyl diester-amide. 4 for compositions containing di- (Z-ethylhexyl) phthalate, and 10.9 for compositions containing tricresyl phosphate. In terms of product performance this means that plasticized illms containing the 2-ethylhexyl diester-amide will stiilen less in cool weather, and show less in- The diester-amides also exert a stabilizing ac-'- tion on vinyl resins containing combined vinyl chloride. They mitigate the deleterious effects which iron pigments normally have on these resins, and they may be used in plastic compositions containing such iron pigments. The diesteramids are also eflective plasticizers and stabilizev ing ingredients in lacquers containing vinyl chloride resins which are to be baked upon iron sur-, faces.

The diester-amides are non-basic materials, and thus they are to be distinguished from the tri-esters oi triethanolamine, which are too basic to serveas plasticizers for vinyl chloride resins, and cause discolorationoi such resins on heating. The diester-amides may themselves cause a slight amount of discoloration of vinyl chloride resins,

but this is not serious. The z-ethylhexyl diester-amide is compatibl with a number oi. vinyl chloride resins over a considerable range, as shown in the table to fol-' low, the compatibilities being determined on iilm cast from solutions.

O-competible.

acvaooo The diester-amides derived from the lower fatty acids, such as propionic acid and butyric acid are more compatible with vinyl chloride-acrylonitrile copolymers than is the 2-ethylhexyl diesteramide. The latter compound is, however, highly compatible with polyvinyl chloride as determined by milling tests at 35% plasticizer concentration.

The diester-amides of diethanolamine or diisopropanolamine and fatty acids containing from 3 to 9 carbon atoms may be prepared by heating the dialkylolamine with at least three moles of a fatty acid at temperatures of about 125 to. 200 C. The heating is preferably conducted under reduced pressure to assist in the removal of the water of condensation, which amounts, to three moles of.

water per mole of the disallwlolamine. Water may also be removed by carrying out the reaction in the presence of a water-immiscible liquid, such as benzene, toluene, xylene or dibutyl ether, and distilling oil! the azeotropic mixture of water and said water-immiscible liquid. If desired, the acid chlorides or acid anhydrides may be employed. In the former instance, hydrochloric acid is formed, and this may be swept out of the reaction vessel by purging with an inert gas, such as carbon dioxide or nitrogen. If the acid anhydride is employed, one mole of free fatty acid is formed for each acyl radical introduced into the dialkylolthe preparation of the plasticizer:

Examrne 1 2,2'iz-ethylhexanamidol diethul dKZ-ethylhewanoate) 105 grams (one mole) of diethanolamine were added slowly to 576 grams (four moles) of 2- ethylhexanoic acid dissolved in 300cc. of xylene. p

This mixture was heated to refluxing temperature under a fractionating column'having a condenser and decanter for separating the xylene and water, which distilled over as the constant boiling mixture. The xylene was returned to the kettle and the water was collected. This procedure was continued for 10 hours at a kettle temperature not exceeding 170' C. until 53 grams (3 moles) of water had been removed. The xylene and excess organic acid were then removed by stripping at 170 C. and 2 mm. Hg pressure in a Claisen type still. The z-ethylhexyl diesteramide was then purified by distillation in a molecular still.

The purified diester-amide has the following physical properties:

Specific gravity at 20/20 C ...0.9554 Boiling point at 5 mm. Hg .255 C.

Vapor pressure at 200 C ...0.6 mm. Hg-

Absolute viscosity at 20 C, .139.2 cp.

Refractive index at 20 C. N .1.458,4

' Solubility in water at 20 C .0.01% by weight Solubility of water in at 20 C. .0.5% by weight v The same compound was also prepared by mixing 105 grams (1 mole) of diethanolamine with e" The residue was stripped in a Claisen type still for 2.5 hours at 150 C. and 5 mm. Hg pressure.

The final product was a viscous, light-colored liquid.

. Exaurtn2 2,2 buturamidodiethyl dibutyrate This compound was prepared by slowly adding 157 grams (1.5 moles) of diethanolamine to 237 grams (1.5 moles) of butyric anhydride accompanied by stirring and-cooling to maintain the temperature at C. This mixture was then added to 513 grams (3.25 moles) of butyric anhydride at 125 0.. followed by heating of the entire reaction mixture at 140C. for four hours. The resulting product. wasstripped in a Claisen type still to remove the free butyric acid. The diester-amide was then purified by distillation in a molecular still, and a light colored viscous liquid was obtained, having a boiling point of 117 C. at 0.05 mm. Hg pressure, a specific gravity of 1.041 at 20/15, and a refractive index 12 0! 1.4540.

Exams: 3

2,2 (Z-ethylbutyramtdo) diethyl dflz-ethylbutyrate) in a Claisen type still, and the diester-amide was distilled ina molecular still. It was obtained as a clear, viscous light-colored liquid. having a specii'lc gravity of 0,988 at 20/15 and a refractive index a of 1.4563.

EXAMPLE 4 I 2,2 nonanamidodiethzll dincmanoate This'compound was made by slowly adding 497 grams (3.14 moles) of nonanoic acid to 105 grams (1 mole) of diethanolamine dissolved in 400 cc. of xylene. The theoretical amount of water (3 gram-moles) was removed by azeotropic distillation over a period of 12 hours with the kettle temperature maintained at 150 to 173 C.

0 min. Hg, a specific gravity of 0.948 at 20/15, and

heating the mixture at 150 C. under a pressure of point of 183 C. at 0.05 mm.Hg a specific gravity refractive index n of at 20/15 of 0.952, and a 1.4605. A

Examrns 5 2,2 (Z-ethylhexanamido) di-isopropzll d2 (Z-ethylhewanoate) One mole (133 grams) of. di-isopropanolamine was reacted with 576 grams (4.0 moles), of

2-ethylhexanoic acid in the presence of xyleneas a water-removing agent in the manner described in the first part of Example 1. the dehydration, however, being somewhat slower. The diester-amide, after purification in a molecular type still had a boiling point of 156 C. at 0.05

a refractive index 12 of 1.4539.

The productwas compatible with copolymers of vinyl chloride and vinyl acetate containing about 96% vinyl chloride at 33% concentration 30 mm. Hg until 53grams of water were removed. 3 of plasticizer by weight of the composition to at-mew 1 yield a flexible sheet having a flex temperature" of 5.0 C.

The invention is susceptible of modification within the scope of the appended claims.

This application is a division of our copending application Serial No. 666,439, riled May 1, 1946.

We claim: T 1. A plastic composition comprising a vinyl resin predominantly composed of vinyl chloride polymerized therein intimately combined with a plasticizer oi the structure CrHaRrOOCR' 8 resin predominantly composed of vinyl chloride polymerized therein intimately combined with aplasticizer, the plasticizer being the dies'ter-amide of diisopropanolamine and a fatty acid of the structure RCOOH. where R is a branched-chain alkyl radical containing from 5 to '7 carbon atoms.

4. A plastic composition comprising. a copolymer 01 vinyl chloride and vinyl acetate contain- I ing at least 87% by weight of 1 combined vinyl ethanolamine and ture RCOOH, where R is a branched-chain alkyl 25 radical-containing from 5 to T carbon atoms. 3. A plastic composition comprising a vinyl chloride intimately combined with a plastlcizer.-

the plasticizer being the diester-amide of diethanolamine and il-ethylhexanoic acid.

5. A plastic composition comprising polyvinyl chloride intimately combined with a plasticizer, the piasticizer being the diester-amide of diz-ethylhexanoic acid. ERANKHN JOHNSTON. WIILIAMEHENSLEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Name Date Dickey Jan. 10, 1939 Number 

